Polyolefin plastic compositions containing halogenated aryl compounds as flame retardants

ABSTRACT

WHEREIN Z is bromine or chlorine, m and m&#39;&#39; are integers having a value of 1-5, i and i&#39;&#39; are integers having a value of 0-2, R is herein defined, M and M&#39;&#39; are each independent and are from the group oxygen, nitrogen or sulfur with the proviso that M and M&#39;&#39; cannot concurrently be oxygen in both cases, and A is chlorine, cyano, nitro, lower alkoxy, lower alkyl, fluorine, dialkylamino, phenyl, halo-phenyl, benzyl, or halo- benzyl.   Plastic compositions containing polyolefins and halogenated aryl compounds having the formula

United States Patent 1191 Anderson 1*Apr. 29, 1975 POLYOLEFIN PLASTICCOMPOSITIONS [56] References Cited CONTAINING HALOGENATED ARYL U ITEDSTATES PATENTS COMPOUNDS AS FLAME RETARDANTS 3,385,819 5/1968 Gouinlock260/45.75 R 75 Inventor; A Anderson, Alma, i 3,560,441 2/l97l Schwarczet al. 260/45.7 R 3,658,634 4/1972 Yanagi et al....... l6l/403 ASSIgHeeIMichigan Chemical Corporation, 3,717,609 2/1973 Kutner 260/45.95 0

Louis, Mich.

Primary E.\'aminerM. J. Welsh 1 Nonce The Porno of h term of Attorney,Agent, or FirmRobert M. Phipps; James .I.

patent subsequent to July 16, 1991, Mullen. Robert S Frieman has beendisclaimed.

[57] ABSTRACT [22] Flled' 1973 Plastic compositions containingpolyolefins and halo- [21] Appl. No.: 330,824 genated aryl compoundshaving the formula Ai I 1 2 M R M' Q z I Related U.S. Application Datawherein Z is bromine or chlorine, m and m are inte- [63]Continuation-impart 6f Ser. N6. 260,240, June 6, g s a i g a value of iand i ar nt g rs ha ing 1972, abandoned. a value of 0-2, R is hereindefined, M and M are each independent and are from the group oxygen,nitrogen [52] U.S. Cl 260/45.9 R; 260/42; 260/42.22; or sulfur with theproviso that M and M cannot con- 260/45.75 R currently be oxygen in bothcases, and A is chlorine, [51] Int. Cl. C08f 45/60 cyano, nitro, loweralkoxy, lower alkyl, fluorine, dial- [58] Field of Search. 260/45.95 G,2.5 A], 45.95 C. kylamino, phenyl, halo-phenyl, benzyl, or haloben-260/613 B, 33.2 R, 45.9 R, DIG. 24; 106/15 FP zyl.

29 Claims, No Drawings POLYOLEFIN PLASTIC COMPOSITIONS CONTAININGHALOGENATED ARYL COMPOUNDS AS FLAME RETARDANTS This application is acontinuation-in-part of copending application Ser. No. 260,240, filedJune 6, 1972 and now abandoned. The entire specification of this case;Ser. No. 260,240, is to be considered as incorporated herein byreference.

The prior art considered in conjunction with the preparation of thisapplication is as follows: US. Pat. Nos. 2,130,990; 2,186,367; 2.329033;3,666,692: 3,686,320; 3,658,634; German Pat. No. 1,139,636; German Pat.No. 2,054,522; Japanese Pat. No. (72) 14,500 as cited in Volume 77.Chemical Abstracts, column l53737k (1972); Chemical Abstracts. Volume13, column 448 Chemical Abstracts. Volume 31, column 7045": and Journalof the Chemical Society, pages 2972-2976 (1963). All of thesepublications are to be considered as incorporated herein by reference.

The present invention relates to plastic compositions containingpolyolefins (including, without limitation, polyethylene andpolypropylene). More specifically, the present invention covers plasticcompositions containing polyolefins and certain halogenated arylcompounds (hereinafter defined) as flame retardants for said plasticcompositions.

Polyolefins and utility thereof are known in the art as exemplified byPolyolefin Plastics, T.O..l. Kresser,

(Van Nostrand Reinhold Plastics Applications Series). Van NostrandReinhold Company, New York, 1969 and Modern Plastics Encyclopedia1972-1973, Vol. 49: No. 10A. October, 1972, pages 78. 83, 85, 86. 89-92,97 and 158-160 and which publications are in toto incorporated herein byreference.

The need for flameretarding polyolefins has also been recognized in theart as exemplified by US. Pat. No. 3,133,038, 3,347,822 and 3.422.048and which publications are in toto incorporated herein by reference.

The resultant disadvantages in the utilization of various prior artmaterials as flame retardants for polyolefins include, withoutlimitation, factors such as thermal migration, heat instability, lightinstability, nonbiodegradable, toxicity, discoloration and the largeamounts employed in order to be effective. Thus, there is always ademand for a material which will function as a flame retardant inpolyolefins and concurrently will not, by incorporation therein,adversely effect the chemical and/or physical and/or mechanicalproperties of the resultant polyolefin plastic composition.

The prior art problem a flame retarded polyolefin composition havingdesired chemical, physical and mechanical properties has now beensubstantially solved by the present invention and the above-describeddisadvantages substantially overcome.

Accordingly, one of the main objects of the present invention is toprovide polyolefin plastic compositions which are flame retarded.

Another object of the present invention is to provide a material forpolyolefin plastic compositions which will not substantially adverselyeffect the chemical and- /0r physical and/or mechanical properties ofsaid compositions.

A further object of the present invention is to provide a flameretardant which is economic and easy to incorporate into polyolefinplastics without being degraded or decomposed as a result of blending orprocessing operations.

It has been found that the foregoing objects can be obtained by theincorporation of a new class of halogenated aryl compounds in olyolefinsto subsequently provide flame retarded compositions which exhibitoutstanding chemical, physical and mechanical properties.

The halogenated aryl compounds used in the present inventioncompositions have the formula:

ln Formula 1 above, Z is bromine or chlorine, in and m are integers eachindependently having a value of l-S; i and i are integers eachindependently having a value of 0-2: M and M are each independent andare from the group oxygen. nitrogen and sulfur with the proviso that Mand M cannot concurrently be oxygen in both cases and where M and/or Mis nitrogen, the formula is A is from the group chlorine, cyano (-CN),nitro (-NO lower alkoxy (e.g. -OCH OC HS). lower alkyl (e.g. CH C H C HC,H,,), fluorine, dialkylamino e.g. N(CH;,) N(C H,-,) phenyl (C,;Hhalophenyl, benzyl (CH- C,,H and halo-benzyl', and R is from the groupalkylene: branched or straight or halo-branched chain group having fromone to six carbon atoms (e.g. CH2, c a C3116, c 11 -C(CH3)H-, -(ca )c(cawhere w 1-6 where X H, Cl, Br

where S saturated ring polymeric systems to make the resultant polymerflame It is to be understood that all of the compounds fall- 25retardantlllustrative (but without limitation) of some of the presentinvention halogenated aryl compounds are shown below:

3 CH CH(0A) CH (c) CH CH(CH H0) d) (cn 0 H CH CH f) CH -C(O) CH (8) CHon @D H C CH ln Formula L i m or i m is not greater than 5.

ing within the above Formula I and as heretofore defined are geneticallydescribed herein as halogenated aryl? compounds.

Com- -pound Nn.

The halogenated aryl compounds are found to be compatible with andeffective additives for various ONNN ON NSSSNNO O NNON NON NON NNNSSSOTable I-Continued cowipeu d No, Z m m' A i i R M M' 9.02 Br 2 2 0 0 s s203 01 2 0 0 N s 20.1 Br 2 2 -CN 1 1 I :11 s 0 205 Br 2 2 --1:0 1 1 2 20 N Br 2 2 0c:1 1 1 2 2 1-1 11 207 Dr 3 3 -0ca 1' CH2 0 11 20s Br 2 2411 1 1 H C- e11 3 s 209 B1: 2 2 F 1 1 CH 0 s 2111 Br 2 2 -N(ca 1 1 H2 HN N 7311. Z. 635 ,H2 2 5 S 212 Br 2 2 -C H B1.2 l l 2 2 N Q? 213 Br 2 2411 0 11 1 v 1 N- s 21 1 Br 2 2 41152 11 315 1 1 Z Z N 215 Br 3 3 -c ,Hc1 1 1 s s 215 c1 3 3 F 1 1 2 N N 217 c1 2 2' -01: 2 2 :1 0

2111 Br 4 o p o Hzc 11 s 219 c1 3 3 -C H Br 1 1 H29 o 220 C1 3 3 -N0 2,2 S 5 2:21 c1 2 2 -0ca 1 1 H c-{S}- 011 s 11 '22 c1. 5 4 411 1 1 HZC 7 N1* 2: 53 c1 3' F 2 '2" 112C 0 a 2 1 Br 1 l C4H9 1 l HZC $611., N O 225Br 1 1 -oc 11 1 1 2C s%- :1 1-1 lngeneral, .thehalogenated compounds arepre- 60 as ketones (e.g. acetone, methyl ethyl ketone, and metpared byreacting a halogenated phenol thiophenol or hyl iso-butyl ketone),alcohols (e.g. methanol, ethanol, aryl amine with a halogenated alkan atelevated temiso-propyl alcohol, butyl alcohol and glycols), aqueousperatures in the presence of a basic material such as alsolvent (e.g.water, a mixture of water and alcohol and kali metal hydroxides,carbonates,bicarbonates, oxides a mixture of water and ketone), andpolar aprotic soland hydrides. The preferred alkali metals are potassiumand sodium. Where one desires to increase, for example, ease of handlingthe reaction mass, solvents such vents such as dimethylformamide (DMF),dimethyl sulfoxide DMSO) and ethers such as tetrahydrofuran (Tl-IF), canbe employed. The desired end product i.e.

the halogenated aryl compound, can be recovered from the reaction massvia various methods such as distillation or crystallization. Where theend product requires recovery via crystallization, various aromaticsolvents such as benzene, toluene, xylene, dichlorobenzene and the likecan be used.

Specifically, the symmetrical halogenated aryl compounds are prepared,for example, according to the following reactions:

The above-described processes can be carried out with conventional,readily available chemical processing equipment. For example, aconventional glasslinked vessel provided with heat transfer means, areflux condenser and a mechanical stirrer can be advantageously utilizedin practicing any of the preferred embodiments of the inventiondescribed in the examples set forth herein. The above describedprocesses and resultant products, i.e., the halogenated aryl compounds,

base sa x-R-x (111) I A1 A1 z O s R. s Z v In the above reaction, X ishalogen, preferably chlorine and R is the same as defined herein. Wherem and m and i and i are different integers, then equivalent molarportions of the particular halogenated phenol, thiophenol or aryl amineare used with equivalent portions of dissimilar halogenated phenol,thiophenol or aryl amine.

The unsymmetrical halogenated aryl compounds are prepared, for example,according to the following reactions:

Inthe above reaction, X and R are the same as mentioned above. The abovereactions are conducted at temperatures ranging from the freezing pointof the initial reaction mass to the boiling point thereof. Preferablythe temperatures are from about 40 C to about 200 C and more preferablyfrom about 50 C to about 175 C. It is to be understood that the reactioncan be conducted under sub atmospheric (e.g. l/l-8/l0 atmospheres),atmospheric or super-atmospheric (e.g. 1.5- atmospheres) pressure.Preferably, the reaction is carried out at atmospheric pressure.

are more fully described in the present applicants copending patentapplication Ser. No. 330,838 filed Feb. 8, 1973, and which isincorporated herein by reference.

The amount of halogenated aryl compound in the present inventioncompositions is any quantity which will effectively render thepolyolefin containing composition flame retardant. In general, theamount used is from about 1 to 25 percent by weight, based on the totalweight of the composition. Preferably, the amount employed is from about5 to about 20 percent by ORX weight. It is to be understood that anyamount can be used as long as it does not substantially adversely effectthe chemical and/or physical and/or mechanical properties of the endpolymer composition. The amount utilized, however, is such amount whichachieves the objectives described herein.

It is to be understood that the term polyolefins as used herein meansbutylene polymers, ethylene polymers (such as low and high densitypolyethylene), olefin polymers, and propylene polymers (such aspolypropylene), including crosslinked, filled and/or reinforced versionsof the same.

Butylene polymers include, without limitation, those derived from themonomers l -butene (H C=CHCH CH 2-butene (CH CH=CH iso butylene (Cl-lC=Cl-l 3-methyl-l-butene (H C=CHCH(CH and cyclobutene (HC=CHCH CHEthylene polymers include, without limitation, polymers of the formula(CH CH with various degrees of wide branches and including polyethylene(high and low density), crosslinked polyethylene, wax blends,ethylene-vinyl acetate copolymers and blends, ethylene-alkyl acrylatecopolymers and blends, carboxylcontaining ethylene copolymers, ionomers,and other derivatives of polyethylene.

Olefin polymers are those polymers derived from higher olefins such as CC,

Propylene polymers include, without limitation, the crystallinehomopolymers of propylene including oxidized, chemically modified, andgraft modified propylene polymers and polypropylene.

Thus the polyolefins used in the present invention composition is anypolyolefin herein defined and which one so desired to flame retard. Itis to be understood that the polyolefins used can be a virgin" material,i.e. substantially free of additives such as stabilizers, plasticizers,dyes, pigments, fillers, and the like, or the polyolefins can haveadditives (such as those mentioned and described herein) alreadycontained therein or added concurrently with or after the addition ofthe halogenated aryl compounds.

Another facet of the present invention relates to the use of certainmetal compounds with the halogenated aryl compounds to promote acooperative effect therebetween and thus enhance the flame retardancy ofthe resultant plastic composition as compared to the flame retardancy ofeither one component used separately. These enhancing agents are fromthe group antimony, arsenic, bismuth, tin and zinc-containing compounds.Without limitation, examples of said enhancing agents include Sb O SbClSbBr Sbl SbOCl, As O AS ZnBO BaB O .l-l O, 2.ZnO.3B O .3.5- H 0 andstannous oxide hydrate. The preferred enhancing agent is antimonytrioxide.

the amount of enchancing agent employed in the present inventioncompositions is any amount which when used with said halogenated arylcompounds will promote a cooperative effect therebetween. In general,the amount employed is from about 1 percent to about percent preferablyfrom about 2 percent to about 10 percent, by weight, based on the totalweight of plastic composition. Higher amounts can be used as long as thedesired end result is achieved.

lt is also within the scope of the present invention to employ othermaterials in the present invention compositions where one so desires toachieve a particular end result. Such materials include, withoutlimitation, adhesion promotors; antioxidants; antistatic agents;antimicrobials; colorants; flame retardants such as those listed onpages 456-458, Modern Plastics Encyclopedia, ibid, (in addition to thenew class of flame retardants described herein); heat stabilizers; lightstabilizers; pigments; plasticizers; preservatives; ultravioletstabilizers and fillers.

In this latter category, i.e. fillers, there can be mentioned withoutlimitation, materials such as glass; carb0l'l; cellulosic fillers (woodflour, cork and shell flour);

calcium carbonate (chalk, limestone, and precipitated calciumcarbonate); metal flakes; metallic oxides (aluminum,-beryllium oxide andmagnesia); metallic powders (aluminum, bronze, lead, stainless steel andzinc); polymers (comminuted polymers and elastomer-plastic blends);silica products (diatomaceous eanh, novaculite, quartz, sand, tripoli,fumed colloidal silica, silica aerogel, wet process silica); silicates(asbestos. kaolimite, mica, nepheline syenite, talc, wollastonite,aluminum silicate and calcium silicate); and inorganic compounds such asbarium ferrite, barium sulfate, molybdenum disulfide and siliconcarbide.

The above mentioned materials, including fillers, are more fullydescribed in Modern Plastics Encyclopedia, ibid, and which publicationis incorporated herein (in toto) by reference.

The amount of the above described materials employed in the presentinvention composition can be any quantity which will not substantiallyadversely effect the desired results derived from the present inventioncompositions. Thus, the amount used can be zero (0) percent, based onthe total weight of the composition, up to that percent at which thecomposition can still be classified as a plastic. In general, suchamount will be from about 0 percent to about percent and specificallyabout 1 percent to about 50 percent.

The halogenated aryl compounds can be incorporated in to the polyolefinsat any processing stage in order to prepare the present inventioncompositions. In general, this is undertaken prior to fabrication eitherby physical blending or during the process of forming polyolefins perse. Where one so desires, the halogenated aryl compounds may bemicronized into finely divided particles prior to incorporation into thepolyolefins.

EXAMPLE l T he resultant mixture is heated to about 245 C.; at

this temperature, it is in a molten state. The percentages by weight ofeach component utilized in the respective formulations are listed inTable II. Each formulation is discharged from the mixer and upon coolingsolidifies and is ground into chips. The chips are subjected tocompression molding in a Wabash press by placing said chips between twoplatens, the bottom of which contains four equal size depressions 3inches by five inches by one-eighth inch deep. The top platen is thenplaced over the bottom platen and heat transfer means supplied theretoin order to melt said chips and thus provide solid samples (aftercooling) for testing.

Portions of the solid samples of each respective formulation (Nos. 1-26)prepared according to the above described procedure are then subjectedto two differ- .ent standard flammability tests, i.e. UL 94 and ASTMD-2863-70. The UL 94 is, in general, the application of a burner to atest specimen (strip) for a certain period of time and observation ofcombustion, burning, extinguishment. This procedure is fully set forthin Underwriters Laboratories bulletin entitled UL 94, Standard forSafety, First Edition, September 1972 and which is incorporated hereinby reference. ASTM No. D-2863- 70 is 'a flammability test whichcorrelates the flammability of a plastic specimen to the availableoxygen in its immediate environment; this correlation is stated as anOxygen Index, 0.1., level predicated upon the percent oxygen in thegaseous medium which is required to just provide a steady state ofcontinuous burning of the plastic specimen. This ASTM method is fullydescribed in 1971 Annual Book of ASTM Standards Part 27, published bythe American Society For Testing and Materials, 1916 Race Street,Philadelphia, Pa.; this publication is to be consider as incorporated(in toto) herein by reference.

The results of these flammability tests are shown in Table 11.

TABLE II FLAMMABILITY DATA FOR POLYPROPYLENE PLASTIC COMPOSITIONSCONTAINING HALOGENATED ARYL COMPOUNDS Formula- Halogenated EnhancingOxygen tion Aryl Compound Agent Index UL 94 No. No. fr Sb O: 71 7:

l. 0 18.0 Burns 2. l 20 0 20.5 SB 3. 1 20 25.0 SB 4. 2 0 19.5 SB 5. 2 2010 23.0 SB 6. 3 20 0 19.0 SB 7. 3 20 10 24.0 SB 8. 4 20 0 19.5 SB 9. 420 10 25.0 SB 10. 32 20 0 21.0 SB 11. 32 20 10 27.5 SE-2 12. 37 20 019.0 SB 13. 37 20 10 23.5 SB 14. 65 20 0 19.5 SB 15. 65 20 10 23.0 SB16. 79 20 0 195 SB 17. 79 20 10 24.0 SB 18. 122 20 0 19.5 SB 19. 122 2010 23.0 SB 20. 143 20 0 21.0 SB 21. 22. 159 20 0 19.5 SB 23. 159 20 1024.0 $8 24. I81 20 0 19.0 SB 25. 181 20 10 23.0 SB 26. 205 20 10 26.5 SB

Referring to Table II, the halogenated aryl compound number relates tothe structural formulae heretofor set forth in Table l; a difference of2% in the Oxygen Index values is considered significant; and the UL 94values are on a graduated scale wherein the highest degree to lowestdegree of flame retardancy is respectively SE-O, SE-l, SE-2, SB andBurns.

The results shown in Table II demonstrate the unique effectiveness ofthese halogenated aryl compounds as flame retardants for polypropylene.Specifically, formulation No. 1 (the control) had a 0.1. of 18.0 and UL94 value of Burns. In Nos. 2, 4, 6, 8, 10, 12, l4, l6, 18, 20, 22 and24, the use of the particular halogenated aryl compound results in asignificant increase (1.03.0 percent increase) in fire retardancy asmeasured by 0.]. (While these formulations had a SB rating, UL 94, theindividual U.L. rating has a wide range-of values and thus the 0.1.number in this case,'more indicative of increased flame retardancy).

The use of an enhancing agent such as Sb O to promote a cooperativeeffect between such agent and the halogenated aryl compound is fullydemonstrated via the results obtained from testing formulation Nos. 3,5, 7, 9,11,13,l5,l7,19, 21, 23, 25 and 26. The highest UL 94 ratings andsignificantly higher 0.1. values (50-105 percent increase) are obtained.

EXAMPLE II Example I is repeated twoce; once using a 10 percenthalogenated aryl compound level and 3 percent Sb O level and secondly,15 percent and 5 percent levels respectively. At both levels, the 0.].values and UL 94 ratings are slightly lower than the 20/10 percentlevels of Example I.

EXAMPLE III Portions of the solid samples of Formulation Nos. 1-26prepared according to the above described procedure of Example 1 aresubjected to the following ASTM tests in order to ascertain otherproperties of the resultant plastic composition:

( l Tensile Strength (at break) ASTM Test No. D63861T; (2) FlexuralStrength ASTM Test No. D790-63; (3) Flexural Modulus ASTM Test No.D790-63; (4) Notched Izod Impact ASTM Test No. D256-56: and (5) HeatDistortion Temperature (HDT) ASTM Test No. D64856.

Each of the aforementioned ASTM tests are standard tests in the art andare utilized collectively in order to ascertain the efficacy of apolymeric system as an overall flame retarded composition for commercialapplication. All of these ASTM Tests are to be considered asincorporated herein by reference.

The results of these ASTM tests show that the physical properties of thepresent invention compositions are basically the same (except 0.]. andUL 94 values) as the plastic material without the flame retardant (i.e.formulation No. 1). Thus, there is no substantial adverse effect on thephysical properties of the plastic material when the novel compounds areincorporated therein.

EXAMPLE IV The procedure of Examples 1 and III are repeated ex-' ceptthat the enhancing agent used is zinc borate instead of Sb- OSubstantially the same results are obtained using zinc borate as thoseobtained using Sb O EXAMPLE V discoloration in any strip tested andwhich demon strates that the present invention compositions are highlyresistant to deterioration by light.

EXAMPLEVI 7 Samples of each of Formulation l. .(c o'ntrol) through 26Table "are subjected to temperature thermal) stability tests via the"use of thermal gravimetric analysis (T GA). This test employed the useofa Thermal Balance, model TGS-l, PerkinElmer Corporation, Norwalk, Conn.and an electrical balance, Cahn 2580 model, Cahn InstrumentC ompany,Paramount, California. The results of these tests show "that thehalogenated aryl containing Formulations had more than adequatestability for melt processing and subsequent heat aging (i.e. hightemperature applications) and thus demonstrating that the particularhalogenated aryls are quite compatible with the polypropylene material.The halogenated aryl stability thus aids in providing sufficient flameretardancy at the polypropylene decomposition temperature. This testalso demonstrates that the halogenated aryls do not exhibit migrationsEXAMPLE VII Examples I VI are repeated again utilizing a low 18 ality ofany particular material in any polymer system until it is activelyundergone incorporation therein and the resultant plastic compositiontested according to various ASTM Standards. Furthermore, it isnecessary, in order to have commercial utility. that the resultant flameretarded plastic composition posess characteristics such as beingnon-toxic. Use of these compounds in the plastic material hasaccomplished all of these objectives.

The above examples have been described in the foregoing specificationfor the purpose of illustration and not limitation. Many othermodifications and ramifications will naturally suggest themselves tothose skilled in the art based on this disclosure. These are intendeddensity polyethylene plastic material as the base resin instead of thepolypropylene material. The results obtained from the repeat of theseexamples show that the halogenated aryls are effective in providingflame retarded polyethylene composition which has commercialapplication.

EXAMPLE VIII Examples I VI are repeated again utilizing a high densitypolyethylene plastic material as the base resin instead of thepolypropylene material. The results obtained from the repeat of theseexamples show that the halogenated aryls are effective in providingflame retarded polyethylene composition which has commercialapplication.

In view of the foregoing Examples and remarks, it is seen that theplastic compositions. which incorporate these compounds. possesscharacteristics which have been unobtainable in the prior art. Thus. theuse of these compounds in the above described plastic material as flameretardants therefor is quite unique since it is not possible to predictthe effectiveness and functionto be comprehended as within the scope ofthis invention.

What is claimed is:

l. A plastic composition containing polyolefm having incorporatedtherein a flame retardant which is a halogenated aryl compound havingthe formula:

wherein Z is selected from the group consisting of bromine or chlorine;m and m are integers having a value of 1-5; 1' and i are integers havinga value of 0-2; M and M are each independent and are selected from thegroup consisting of oxygen, nitrogen or sulfur with the proviso that Mand M cannot concurrently be oxygen in both cases and where M and/or Mis nitrogen. the formula is A is selected from the group consisting ofchlorine,

cyanno, nitro, lower alkozy, lower alkyl, fluorine, dialkylamino,phenyl, halo-phenyl, benzyl, or halobenzyl; and R is selected from thegroup consisting of (a) alkylene group having from one to six carbonatoms (b) ca ca(0a) c11 (c) CH CIKCH OII) .CH

(cl) (CH 0 (CH where w 1-6 X where X ll, Cl, Br

0 CH2 Q (f) 011 c(o) cu (g) CH CII where S saturated ring 19 20 2. Thecomposition as set forth in claim 1 wherein i 6. The composition as setforth in claim 5 wherein i and i are both 0. and i are both 0.

3. The composition as set forth in claim 1 wherein i 7. The compositionas set forth in claim 5 wherein i and i are both 1. and i are both 1.

4. The composition as set forth in claim 1 wherein i s 8. Thecomposition as set forth in claim 5 wherein i and i are both 2. and iare both 2.

5. A plastic composition containing polyolefin having 9. The compositionas set forth in claim 6 wherein R incorporated therein a flame retardantwhich is a halois an alkylene group having from I to 6 carbon atoms.genated aryl compound having the formula; 10. A plastic compositioncontaining polyolefin hav- A A1 I Z S R S Z i wherein Z is selected fromthe group consisting of bro- 2O ing incorporated therein a flameretardant which is a mine or chlorine; m and m are integers having avalue halogenated aryl compound having the formula:

. H a H r Z N R N I of 1-5; i and i are integers having a value of 0-2;A is wherein Z is selected from the group consisting of broselected fromthe group consisting of chlorine. cyano. mine or chlorine; m and m areintegers having a value nitro. lower alkoxy lower alkyl fluorine.dialkylamino. of 1-5; 1' and i are integers having a value of 0-2; A isphenyl. halo-phenyl, benzyl, or halobenzyl; and R is selected from thegroup consisting of chlorine, cyano, selected form the group consistingof nitro. lower alkoxy. lower alkyl. fluorine, dialkylamino (a) alkylenegroup having from one to six carbon atoms (b) CH CH(0H) CH 0 W where w1-6 'where X H, Cl, Br n a 4 (f) CH- C(0)' -CH (g) 011 CH where Ssaturated phenyl halo-phenyl. benzyl or halobenzyl; and R is sewhereinz'is bromine jor, chlorine, m and m are integers lected from the groupconsisting of having a value of l -5, i and i'are integers having a (a)alkylene group having from one to six carbon atoms (c) cu Cli(CH OH) c11v i n where X a H, Cl, Br

n 4 CH 9}- CH2 (f) cH2 (0)- (:2

(g) 011 cu where S saturatedii c c11 ring ll. The composition as setforth in claim 10 wherein value of 0-2; A is chlorine, cyano, nitro,lower alkoxy,

i and i are both 0. lower alkyl, fluorine, dialkylamino, phenyl, halo-12. The composition as set forth in claim 10 wherein phenyl, benzyl, orhalobenzyl; and R is selected from i and i are both 1. the groupconsisting of (a) alkylene group having from one to six carbon atoms (b)Cli Cl-I(0l-l) CH e r ware:

(d) (CH 0 (CH where w 1-6 (e) 4 x where x a, Cl, Br

CH 0 CH (f) ca c(o) c11 (3) CH gr) CH where S saturated 2 2 ring 13. Thecomposition as set forth in claim 10 wherein 16. The composition as setforth in claim 15 wherein iandi are both 2. i and are both 0.

17. The composition as set forth in claim 15 wherein i and i are both 1.

18. The composition as set forth in claim 15 wherein i and i are both 2.1

15. A plastic composition containing polyolefin hav- 19. The compositionas set forth in claim 16 wherein ing incorporated therein a flameretardant which is a R is an alkylene group having from 1 to 6 carbonhalogenated aryl compound having the formula: atoms.

14. The composition as set forth in claim 11 wherein R is an alkylenegroup having from 1 to 6 carbon atoms.

A1 A l wherein Z is bromine or chlorine. m and m are integers having avalue of 1-5; i and i are integers having a value of 0-2; A is chlorine,cyano, nitro. lower alkoxy. 15

lower alkyl. fluorine; dialkylamino. phenyl. halophenyl, benzyl, orhalobenzyl; and R is selected from the group consisting of 23. Thecomposition as set forth in claim 20 wherein iand i are both 2.

24. The composition as set forth in claim 21 wherein R is an alkylenegroup having from 1 to 6 carbon atoms.

25. A plastic composition containing polyolefm having incorporatedtherein a flame retardant which is a halogenated aryl compound havingthe formula:

A A l S-R-0 Zr wherein Z is bromine or chlorine, m and m are integershaving a value of 1-5; i and i are integers having a (a) alkylene grouphaving from one to six carbon atoms cn CH2 (f) cn 0(0) CH2 2]. Thecomposition as set forth in claim 20 wherein [and i are both 0.

22. The composition as set forth in claim 20 wherein [and i are both l.

where w B 1-6 where X H, Cl, Br

where S saturated ring value of 0-2; A is chlorine, cyano, nitro, loweralkoxy,

4 lower alkyl, fluorine, dialkylamino, phenyl, halophenyl, benzyl, orhalobenzyl; and R is selected from the group consisting of (a) alkylenegroup having from one to six carbon atoms (b) CH --CH(OH) CH (c) 0:1CH(CH20H) 011 where w 1-6 where X H, Cl, Br

(g) cH on where S saturated ring 26. The composition as set forth inclaim 25 wherein i and i areboth 2. i and i are both 0. 29. Thecomposition as set forth in claim 26 wherein 27. The composition as setforth in claim 25 wherein R is an alkyiene group having from 1 to 6carbon i and i' are both i. atoms.

28. The composition as set forth in claim 25 wherein t a

1. A PLASTIC COMPOSITION CONTAINING POLYOLEFIN HAVING INCORPORTEDTHEREIN A FLAME RETARDANT WHICH IS A HALOGENATED ARYL COMPOUND HAVINGTHE FORMULA:
 2. The composition as set forth in claim 1 wherein i andi'' are both
 0. 3. The composition as set forth in claim 1 wherein i andi'' are both
 1. 4. The composition as set forth in claim 1 wherein i andi'' are both
 2. 5. A plastic composition containing polyolefin havingincorporated therein a flame retardant which is a halogenated arylcompound having the formula;
 6. The composition as set forth in claim 5wherein i and i'' are both
 0. 7. The composition as set forth in claim 5wherein i and i'' are both
 1. 8. The composition as set forth in claim 5wherein i and i'' are both
 2. 9. The composition as set forth in claim 6wherein R is an alkylene group having from 1 to 6 carbon atoms.
 10. Aplastic composition containing polyolefin having incorporated therein aflame retardant which is a halogenated aryl compound having the formula:11. The composition as set forth in claim 10 wherein i and i'' are both0.
 12. The composition as set forth in claim 10 wherein i and i'' areboth
 1. 13. The composition as set forth in claim 10 wherein i and i''are both
 2. 14. The composition as set forth in claim 11 wherein R is analkylene group having from 1 to 6 carbon atoms.
 15. A plasticcomposition containing polyolefin having incorporated therein a flameretardant which is a halogenated aryl compound having the formula: 16.The composition as set forth in claim 15 wherein i and '' are both 0.17. The composition as set forth in claim 15 wherein i and i'' areboth
 1. 18. The composition as set forth in claim 15 wherein i and i''are both
 2. 19. The composition as set forth in claim 16 wherein R is analkylene group having from 1 to 6 carbon atoms.
 20. A plasticcomposition containing polyolefin having incorporated therein a flameretardant which is a halogenated aryl compound having the formula: 21.The composition as set forth in claim 20 wherein i and i'' are both 0.22. The composition as set forth in claim 20 wherein i and i'' areboth
 1. 23. The composition as set forth in claim 20 wherein i and i''are both
 2. 24. The composition as set forth in claim 21 wherein R is analkylene group having from 1 to 6 carbon atoms.
 25. A plasticcomposition containing polyolefin having incorporated therein a flameretardant which is a halogenated aryl compound having the formula: 26.The composition as set forth in claim 25 wherein i and i'' are both 0.27. The composition as set forth in claim 25 wherein i and i'' areboth
 1. 28. The composition as set forth in claim 25 wherein i and i''are both
 2. 29. The composition as set forth in claim 26 wherein R is analkylene group having from 1 to 6 carbon atoms.